Ether-esters of sucrose



. product in substantially quantitative yields.

sired product may be employed as thus obtainedor Z T 60 polyoxyalkylcne chain is a series of oxyethylene, -propyl- 2,927,919 ETHER-ESTERSfOF SUCROSE Arthur W. Anderson, Midland, Mich., ass'ignor to The v'Dow1C-hemical Company, Midland, .Mich., a corporaa tion-pf Delaware N Drawing. Application December so, 1951 I V. -SeriaiNQ'JO'SJBrsi'z'ciams. (c1. 2 0 -209 The present invention relates -to -ether-esters ofpcar-f boxtylic. acids and is more particularly concerned with new and useful compoundshaving the general {formula Fatented, Mar. 8, 196i) ice The following examples are illustrative of the flpresent invention but are not to be construed as limiting.

Example 1 I 4.4 grams of 2,4,S-trichlorophenoxyacetic acid, j grams (1.0 molar; equivalent) of diglycidyl ether of polyoxyethylene glycol (polyglycol having average molecular weight 400), 12.2 grams (1 molar equivalent) and heated ina steam bath at 85 C. for 6 hours. The product, an amber colored, syrupy liquid was analyzed and found -to contain 0.4 percent free acid, and 4.4 a

percent unreacted'di'glycidyl ether of the pol-yglycol.- It was soluble in 'water and was found to be eifectiveas a herbicide exhibiting 98 and 99 percent control of Brasysica rapus and Phalaris canarensis, respectively, when applied to the living vegetation as an aqueous selfi "'"Q E Q emulsifying solution at a concentration of IOQparts H i H wherein R represents a hydrocarbon radical having from -1 to 19 carbon atoms, inclusive, which may, contain,

halogen substituents thereon, 'R' represents aihydrojxyper million of. active ingredient.

:In the manner of the foregoing example substituting the various others, acids and hydroxyalkylsucroses other compounds :of thejpresent invention can .be prepared. The results of such substitution and the properties of -Z'so"rne .of the products produced are set forth below:

JReactants (1 mol each) Water Solubility Remarks Diglycidyl Ether of" Acid Employed v Sucrose Ether Polyglyopl Having a; v Molecular Weight of Steario Hydroxycthyl (10 'E.'O./mol) Polyethylene 490.. Soluble Surface active. 2,4,fi-trichlorophenoxyacetie Hydroxypropyl (8 P.0./mol). Polypropyleno'400-..; Self 'dispersible Surface activc'herblcidal.

Dn 'iin r"in :Snlnlila D0,, :Acetylsalioylici dn Surface active fungicidal. D0. .JJ. Elydroxy thylfim E 0 /mol) d0 Slightly fungicidal. Bromoacetic do Slightly herbicidal. 2,4-dichloropheuoxy Patio do Herbicidal antimicrobial. 3,4-dichlorophenoxyacetlc do Herbicidal. 2(2,4,6-trichlorophenoxy)prop do Herbicidal antimicrobial. 4(2,4-dichlorophenoxy) butyric--- do Slightly active. -chlorootoloxyacetic do Hcrbicidal antimicrobial. 2,2-dichloropropionjcl0 oxyalkylene' groups per mole of sucrose), R' represents an alkylene radical having from 2 to 4 carbon monocarboxylic acid can be employed in'accordance atoms, inclusive, and. n represents an integer from 2 to glycol with an equimolarv amount of a hydroxyalkylsucrose and an equimolar amount of an appropriate acid in the presence of a suitable catalyst. The reaction proceeds smoothly at temperatures from room temperature to about 120 C. with the production of the desired The depurified by conventional manner.

In making the compounds-of the present invention; a diglycidyl etherof a polyglycol, an equirnolar portion of hydroxyalkylsucrose and an equimolar portion of an organic acid are mixed or otherwise blended together Herbicidal'.

It is to be understood that any aliphatic or aromatic with the present invention. Thus, for example, acetic, propionic,-butyric, isobutyric, valeric, isovaleric, pivalic,

caproic, isocaproic, u,fl-dirnethylbutyric, enanthic, isoenanthic, caprylic, pelargonic, capric, hendecanoic, 50 lauric, tridecanoic, myristic, pentadecanoic, palmitic,

margaric, -stearic, nonadecanoic, arachidic, acrylic, crotonic, methylacrylic, tiglic, angelic, senecioic, oleic, linoleic, sorbic, benzoic, toluic, hydrocinnamic, xylic,

phenoxyacetic, acetylsalicylic, phenoxypropionic, phenoxybutyricacids and the like, and their halo and alkylsubstituted derivatives such as 2,4-dichlorophenoxyacetic, 2,4,5 trichlorophenoxyaceticacid, 2,(2,4,6 trichlorophenoxy)propionic acid.

Further, any polyoxyalkylene glycols wherein the cue or -butylene moieties may be employed.

The polyoxyaikylene glycol diglycidyl others used in making the compounds of the presentinvention may be conveniently prepared by the condensation of the polyin the presence of a catalyst such asan aliphatic amine, glycol'with glycidol or, preferably, with epichlorohydrin for example, hexamethylenetetramine, andv at; a temperature of from room temperature to about 120 C.

The reaction is preferably carried out at about 60 to I 100 C. for a period 'of time to complete the reaction. Upon completion of thereaction, the desired product, usually produced in quantitative yields, may be purified by solvent extraction if desired.

in the presence of alkali in the manner commonly used in making glycidyl ethers. I

v The hydroxyalkylsucrose ethers employed in accordance with'the present invention are the hydroxyethyl,

hydroxypropyl and the hydroxybutylsucrose ethers obtainable .by the reaction of from 8 to 10 moles of alkylene oxide with sucrose to etherify at least eachv hydroxyl OH H wherein R represents an organic radical containing from I 1 to 19 carbon atoms inclusive and selectedfro'm the class consisting of monovalent aliphatic radicals and monovalent aromatic radicals of the benzene series, R represents a 'hydroxyalkylsucrose residue containing from 8 to 10 oxyalkylene groups each of said oxyalkylene having from 24 carbon atoms inclusive, R" represents an alkylene radical having from 2 to 4 carbon atoms, in-

clusive, and n represents an integer from inclusive. I

2. An ether-ester of a carboxylic acid as set forth in claim 1 wherein R isan aliphatic radical.

3. An ether-ester of a carboxylic acid as claimed in claim 1 wherein R is a phenoxyaliphatic radical.

4. An ether-ester of a carboxylic acid as claimed in I claim 1 wherein R is a haloaliphatic radical.

5. An ether-ester of a carboxylic acid as claimed in claim 1 where R represents an alkyl radical.

6. An ether-ester of a carboxylic acid as claimed in claim 1 wherein R represents an alkenyl. radical.

7. An ester-ether of a carboxylic acid as claimed Zin i claim 1 wherein R is a 2,4,5-trichlorophenoxyalkyl radia1.

8. An ester-ether of a carboxylicv acid claimed in claim 1 wherein R is a'2,4dichlorophenoxyalkyl radical. 9. An ester-ether of a carboxylic acid as claimed in claim 1 wherein R is a bromomethyl radical.

10. An ester-ether of a carboxylic acid as claimed in claim 1 wherein R' is ethylene and n represents about 10. 11. An ester-ether of a carboxylic acid as claimed in claim 1 where R is propylene and n is about 8.

12. A method for the preparation of a compound having the formula wherein R represents an organic radical containing from 1 to 19 carbon atoms inclusive and selected from the class consisting of monovalent aliphatic radicals and monovalent aromatic radicals of the benzene series, R represents a hydroxyalkylsucrose residue containing about 8 to 10 oxyalkylene groups each of said oxyalkylene having from 2-4 carbon atoms inclusive, R" represents an alkylene radical having from 2 to 4 carbon atoms,

, inclusive, and n represents an integer from 2 to 20 inelusive, which comprises reacting equimolar proportions of a diglycidyl ether of a polyglycol having the formula 0H,0Hci12o R'0)..cHloH0H2 with an organic acid having the formula u RC0H and a hydroxyalkylsucrose having from 8 to 10 oxyalkylene groups per sucrose molecule inthe presence of a catalyst and at a temperature of from C. to C.

References Cited in the file of this patent UNITED STATES PATENTS 2,450,079 Brown Sept. 28, 1948 2,541,142 'Zief et al. 'Feb. 13, 1951 2,602,789 Schwartz et a1. July 8, 1952 FOREIGN PATENTS 495,548 Canada Aug. 25, 1953 

1. AN ETHER-ESTER OF A CARBOXYLIC ACID WHICH HAS THE FORMULA 